Supercapacitor electrode having highly oriented and closely packed expanded graphite flakes and production process

ABSTRACT

Provided is a process for producing a supercapacitor electrode, comprising: (a) preparing a deformable mass of multiple flakes of exfoliated graphite worms or expanded graphite dispersed in or impregnated by a liquid or gel electrolyte; and (b) subjecting the deformable mass to a forced assembling and orientating procedure, forcing the deformable mass to form the electrode, wherein these fakes are spaced by thin electrolyte layers, having an electrolyte layer thickness from 0.4 nm to 10 nm, and the flakes are substantially aligned along a desired direction, and wherein the electrode has a physical density from 0.5 to 1.7 g/cm 3  and a specific surface area from 50 to 3,300 m 2 /g, when measured in a dried state of the flakes without the electrolyte. This process leads to a supercapacitor having a large electrode thickness, high active mass loading, high tap density, and exceptional energy density.

FIELD OF THE INVENTION

The present invention relates generally to the field of supercapacitor and, more particularly, to an exfoliated graphite worm- or expanded graphite-based electrode, a supercapacitor containing such an electrode, and a process for producing same.

BACKGROUND OF THE INVENTION

Electrochemical capacitors (ECs), also known as ultracapacitors or supercapacitors, are being considered for uses in hybrid electric vehicles (EVs) where they can supplement a battery used in an electric car to provide bursts of power needed for rapid acceleration, the biggest technical hurdle to making battery-powered cars commercially viable. A battery would still be used for cruising, but supercapacitors (with their ability to release energy much more quickly than batteries) would kick in whenever the car needs to accelerate for merging, passing, emergency maneuvers, and hill climbing. The EC must also store sufficient energy to provide an acceptable driving range. To be cost-, volume-, and weight-effective compared to additional battery capacity they must combine adequate energy densities (volumetric and gravimetric) and power densities (volumetric and gravimetric) with long cycle life, and meet cost targets as well.

ECs are also gaining acceptance in the electronics industry as system designers become familiar with their attributes and benefits. ECs were originally developed to provide large bursts of driving energy for orbital lasers. In complementary metal oxide semiconductor (CMOS) memory backup applications, for instance, a one-Farad EC having a volume of only one-half cubic inch can replace nickel-cadmium or lithium batteries and provide backup power for months. For a given applied voltage, the stored energy in an EC associated with a given charge is half that storable in a corresponding battery system for passage of the same charge. Nevertheless, ECs are extremely attractive power sources. Compared with batteries, they require no maintenance, offer much higher cycle-life, require a very simple charging circuit, experience no “memory effect,” and are generally much safer. Physical rather than chemical energy storage is the key reason for their safe operation and extraordinarily high cycle-life. Perhaps most importantly, capacitors offer higher power density than batteries.

The high volumetric capacitance density of an EC relative to conventional capacitors (10 to 100 times greater than conventional capacitors) derives from using porous electrodes to create a large effective “plate area” and from storing energy in the diffuse double layer. This double layer, created naturally at a solid-electrolyte interface when voltage is imposed, has a thickness of only about 1 nm, thus forming an extremely small effective “plate separation.” Such a supercapacitor is commonly referred to as an electric double layer capacitor (EDLC). The double layer capacitor is based on a high surface area electrode material, such as activated carbon, immersed in a liquid electrolyte. A polarized double layer is formed at electrode-electrolyte interfaces providing high capacitance. This implies that the specific capacitance of a supercapacitor is directly proportional to the specific surface area of the electrode material. This surface area must be accessible by electrolyte and the resulting interfacial zones must be sufficiently large to accommodate the so-called electric double-layer charges.

In some ECs, stored energy is further augmented by pseudo-capacitance effects, occurring again at the solid-electrolyte interface due to electrochemical phenomena such as the redox charge transfer. Such a supercapacitor is commonly referred to as a pseudo-capacitor or redox supercapacitor. A third type of supercapacitor is a lithium-ion capacitor that contains a pre-lithiated graphite anode, an EDLC cathode (e.g. typically based on activated carbon particles), and a lithium salt electrolyte.

However, there are several serious technical issues associated with current state-of-the-art supercapacitors:

-   (1) Experience with supercapacitors based on activated carbon     electrodes shows that the experimentally measured capacitance is     always much lower than the geometrical capacitance calculated from     the measured surface area and the width of the dipole layer. For     very high surface area activated carbons, typically only about 20-40     percent of the “theoretical” capacitance was observed. This     disappointing performance is related to the presence of micro-pores     (<2 nm, mostly <1 nm) and ascribed to inaccessibility of some pores     by the electrolyte, wetting deficiencies, and/or the inability of a     double layer to form successfully in pores in which the oppositely     charged surfaces are less than about 1-2 nm apart. In activated     carbons, depending on the source of the carbon and the heat     treatment temperature, a surprising amount of surfaces can be in the     form of such micro-pores that are not accessible to liquid     electrolyte. -   (2) Despite the high gravimetric capacitances at the electrode level     (based on active material weights alone) as frequently claimed in     open literature and patent documents, these electrodes unfortunately     fail to provide energy storage devices with high capacities at the     supercapacitor cell or pack level (based on the total cell weight or     pack weight). This is due to the notion that, in these reports, the     actual mass loadings of the electrodes and the apparent densities     for the active materials are too low. In most cases, the active     material mass loadings of the electrodes (areal density) is     significantly lower than 10 mg/cm² (areal density=the amount of     active materials per electrode cross-sectional area along the     electrode thickness direction) and the apparent volume density or     tap density of the active material is typically less than 0.75     g/cm⁻³ (more typically less than 0.5 g/cm⁻³ and most typically less     than 0.3 g/cm⁻³) even for relatively large particles of activated     carbon.     -   The low mass loading is primarily due to the inability to obtain         thicker electrodes (thicker than 150 μm) using the conventional         slurry coating procedure. This is not a trivial task as one         might think, and in reality the electrode thickness is not a         design parameter that can be arbitrarily and freely varied for         the purpose of optimizing the cell performance. Contrarily,         thicker samples tend to become extremely brittle or of poor         structural integrity and would also require the use of large         amounts of binder resin. These problems are particularly acute         for graphene material-based electrodes. It has not been         previously possible to produce graphene-based electrodes that         are thicker than 100 μm and remain highly porous with pores         remaining fully accessible to liquid electrolyte. The low areal         densities and low volume densities (related to thin electrodes         and poor packing density) result in relatively low volumetric         capacitances and low volumetric energy density of the         supercapacitor cells.     -   With the growing demand for more compact and portable energy         storage systems, there is keen interest to increase the         utilization of the volume of the energy storage devices. Novel         electrode materials and designs that enable high volumetric         capacitances and high mass loadings are essential to achieving         improved cell volumetric capacitances and energy densities. -   (3) During the past decade, much work has been conducted to develop     electrode materials with increased volumetric capacitances utilizing     porous carbon-based materials, such as graphene, carbon     nanotube-based composites, porous graphite oxide, and porous meso     carbon. Although these experimental supercapacitors featuring such     electrode materials can be charged and discharged at high rates and     also exhibit large volumetric electrode capacitances (50 to 150     F/cm³ in most cases, based on the electrode volume), their typical     active mass loading of <1 mg/cm², tap density of <0.2 g/cm³, and     electrode thicknesses of up to tens of micrometers (<<100 m) are     still significantly lower than those used in most commercially     available electrochemical capacitors (i.e. 10 mg/cm², 100-200 μm),     which results in energy storage devices with relatively low areal     and volumetric capacitances and low volumetric energy densities. -   (4) For graphene-based supercapacitors, there are additional     problems that remain to be solved. For instance, individual graphene     sheets have a great tendency to re-stack themselves, effectively     reducing the specific surface areas that are accessible by the     electrolyte in a supercapacitor electrode and, hence, reducing the     specific capacitance of the electrode. Further, the tap density of     graphene-based electrode is extremely low, typically lower than 0.3     g/cm³ and more typically lower than 0.1 g/cm³. Furthermore, it has     been very difficult to produce graphene-based electrodes that are     thicker than 75 μm using the conventional slurry coating process.     Such an electrode typically requires a large amount of a binder     resin (hence, significantly reduced active material proportion vs.     non-active or overhead materials/components). In addition, any     graphene- or graphitic material-based electrode prepared in this     manner that is thicker than 50 μm is brittle and weak. There has     been no effective solution to these problems.

Thus, a need exists for an alternative carbon or graphitic material that can form a multi-layer structure having inter-layer pores of adequate sizes. These pores must be sufficiently large to allow for accessibility by the electrolyte and to enable the formation of electric double-layer charges, which presumably require a pore size of at least 0.3-2 nm. However, these pores or inter-layer spacings must also be sufficiently small to ensure a large tap density (hence, large capacitance per unit volume or large volumetric energy density). Unfortunately, the typical tap density of graphene-based and other graphitic material-based electrodes produced by the conventional process is less than 0.3 g/cm³, and most typically <<0.2 g/cm³. To a great extent, the requirement to have large pore sizes and high porosity level and the requirement to have a high tap density are considered mutually exclusive in supercapacitors.

Therefore, there is clear and urgent need for supercapacitors that have high active material mass loading (high areal density), active materials with a high apparent density (high tap density), high electrode thickness, high volumetric capacitance, and high volumetric energy density. One must also overcome problems such as the demand for large proportion of a binder resin, and difficulty in producing thick electrode layers.

Thus, it is an object of the present invention to provide a cost-effective process for mass-producing highly conductive, mechanically robust non-graphene-based graphitic electrodes that do not have these common issues of conventional graphene-based electrodes. This process must also enable the flexible design and control of the porosity level and pore sizes. Specifically, this process enables the production of electrodes that overcome the issues of low tap density, low achievable electrode thickness, low achievable active material mass loading, low specific capacitance (per unit weight or volume), and low gravimetric and volumetric energy densities.

SUMMARY OF THE INVENTION

The present invention provides a process for producing a supercapacitor electrode containing electrolyte-impregnated flakes of exfoliated graphite worms or expanded graphite. The process comprises: (a) preparing a deformable mass of the flakes of exfoliated graphite worms or expanded graphite dispersed in or impregnated by a liquid or gel electrolyte; and (b) subjecting the deformable mass to a forced assembling and orientating procedure, forcing the deformable mass to form the electrode, wherein the flakes are spaced by thin electrolyte layers, having an electrolyte layer thickness from 0.4 nm to 10 nm (preferably and typically <5 nm, more preferably and typically <2 nm), and the flakes are substantially aligned or oriented along a desired direction, and wherein the electrode has a physical density from 0.5 to 1.7 g/cm³ (more typically from 0.7 to 1.3 g/cm³) and a specific surface area from 50 to 3,300 m²/g (more typically from 200 to 2,600 m²/g), when measured in a dried state of the flakes when the electrolyte is not present.

It may be noted that graphite worms are typically produced from thermal exfoliation of graphite intercalation compounds (GIC) or graphite oxide (GO), which are produced by intercalation and/or oxidation of graphite (e.g. by immersing natural graphite particles in a mixture of sulfuric acid and sodium nitrate). Graphite worms are a worm-like mass of “exfoliated/expanded” graphite flakes that remain interconnected. By subjecting graphite worms to a mechanical shearing stress (e.g. an air jet mill, ultrasonication, mechanical stirrer, or disperser treatment), one can break up the interconnections between constituent graphite flakes to obtain “expanded graphite” flakes, having a typical thickness greater than 100 nm. Either graphite worms or expanded graphite flakes can be subjected to physical or chemical activation for obtaining activated graphite flakes having increased specific surface areas and, hence, increased specific capacitance.

In certain embodiments, the graphite flakes have a content of non-carbon elements from 0.1% to 45% by weight. The non-carbon elements may include H, O, N, B, F, Cl, Br, I, or a combination thereof. These non-carbon elements may be imparted onto graphite flakes through doping, chemical functionalization, or chemical reactions.

Preferably, step (a) contains a sub-step of subjecting the flakes of exfoliated graphite worms or expanded graphite to a chemical or physical activation treatment to obtain activated graphite flakes and then dispersing the activated graphite flakes in a liquid or gel electrolyte or impregnating the activated graphite flakes with a liquid or gel electrolyte. The activation treatment of the flakes of exfoliated graphite worms or expanded graphite can increase the specific surface area of these flakes from a typical range of 50-500 m²/g to a typical range of 500-3,300 m²/g, thereby effectively increasing the specific capacitance of a supercapacitor electrode containing such flakes.

The activation treatment can be accomplished through oxidizing, physical activation (e.g. via water steam or CO₂), chemical activation (e.g. KOH or NaOH), or exposure to nitric acid, fluorine, or ammonia plasma, or a combination thereof.

To form a pseudo-capacitor, the graphite flakes (with or without prior activation) may be pre-deposited with a nano-scaled coating (thickness <100 nm) or particles (diameter <100 nm) of a redox pair partner selected from an intrinsically conductive polymer, a transition metal oxide, and/or an organic molecule, wherein a redox pair partner and a graphite flake form a redox pair for pseudo-capacitance. The intrinsically conducting polymer may be selected from polyaniline, polypyrrole, polythiophene, polyfuran, sulfonated polyaniline, sulfonated polypyrrole, sulfonated polythiophene, sulfonated polyfuran, sulfonated polyacetylene, or a combination thereof.

The liquid or gel electrolyte may contain an aqueous electrolyte, an organic electrolyte, an ionic liquid electrolyte, or a mixture of an organic and an ionic electrolyte.

In some desired embodiments, the forced assembling and orientating procedure includes introducing the deformable mass (of the flakes of exfoliated graphite worms or expanded graphite dispersed in or impregnated by a liquid or gel electrolyte), having an initial volume V₁, in a mold cavity cell and driving a piston into the mold cavity cell to reduce the deformable mass volume to a smaller value V₂, allowing excess electrolyte to flow out of the cavity cell and aligning the multiple graphite flakes along a direction at an angle from 0° to 90° relative to a movement direction of the piston.

In some desired embodiments, the forced assembling and orientating procedure includes introducing the deformable mass in a mold cavity cell having an initial volume V₁, and applying a suction pressure through a porous wall of the mold cavity to reduce the deformable mass volume to a smaller value V₂, allowing excess electrolyte to flow out of the cavity cell through the porous wall and aligning the multiple graphite flakes along a direction at an angle from approximately 0° to approximately 90° relative to a suction pressure direction.

In some preferred embodiments, the forced assembling and orientating procedure includes introducing a first layer of the deformable mass of graphite flakes/electrolyte mixture onto a surface of a supporting conveyor and driving the layer of deformable mass supported on the conveyor through at least a pair of pressing rollers to reduce the thickness of the deformable mass layer and align the multiple graphite flakes along a direction parallel to the conveyor surface for forming a layer of electrolyte-impregnated graphite flakes.

The process may further include a step of introducing a second layer of the deformable mass of graphite flakes/electrolyte mixture onto a surface of the layer of electrolyte-impregnated graphite flake structure to form a two-layer graphite flake-electrolyte structure, and driving the two-layer structure through at least a pair of pressing rollers to reduce a thickness of the second layer of deformable mass and align the multiple graphite flakes along a direction parallel to the conveyor surface for forming a layer of electrolyte-impregnated graphite flakes. The same procedure may be repeated by allowing the conveyor to move toward a third set of pressing rollers, depositing additional (third) layer of deformable mass onto the two-layer structure, and forcing the resulting 3-layer structure to go through the gap between the two rollers in the third set to form a further compacted, electrolyte-impregnated graphite flake structure.

The process may further include a step of compressing or roll-pressing the electrolyte-impregnated graphite flake structure to reduce the thickness of thin electrolyte layers (as a spacer disposed between graphite flakes) in the impregnated graphite flake structure, improve orientation of graphite flakes, and squeeze excess electrolyte out of the impregnated graphite flake structure for forming the supercapacitor electrode.

The process may preferably be a roll-to-roll process wherein the forced assembly procedure includes feeding the supporting conveyor, in a continuous film form, from a feeder roller to a deposition zone, continuously or intermittently depositing the graphene dispersion onto a surface of the supporting conveyor film to form a layer of graphene dispersion thereon, and collecting the layer of electrolyte-impregnated laminar graphene structure supported on conveyor film on a collector roller.

The graphene dispersion may contain a graphene oxide dispersion prepared by immersing a graphitic material in a powder or fibrous form in an oxidizing liquid in a reaction vessel at a reaction temperature for a length of time sufficient to obtain the graphene dispersion wherein the graphitic material is selected from natural graphite, artificial graphite, meso-phase carbon, meso-phase pitch, meso-carbon micro-bead, soft carbon, hard carbon, coke, carbon fiber, carbon nano-fiber, carbon nano-tube, or a combination thereof and wherein the graphene oxide has an oxygen content no less than 5% by weight.

The process may further comprise a step of cutting the electrolyte-impregnated laminar graphene structure into multiple sheets and stacking the multiple sheets to form an electrode for a supercapacitor.

In a preferred embodiment, the process may further comprise a step of attaching the electrolyte-impregnated laminar graphene structure to a current collector, wherein the graphene sheets are aligned parallel to a primary surface of the current collector. In another preferred embodiment, the process further comprises a step of attaching the electrolyte-impregnated laminar graphene structure to a current collector, wherein the graphene sheets are aligned perpendicular to a primary surface of the current collector.

The present invention also provides a supercapacitor comprising an anode, a cathode, an ion-permeable separator that electronically separates the anode and the cathode, and an electrolyte in ionic contact with the anode and the cathode, wherein the anode and/or the cathode contains the aforementioned electrolyte-impregnated laminar graphene structure.

In a preferred embodiment, the supercapacitor may further comprise an anode current collector and/or a cathode current collector and the graphene sheets in the electrolyte-impregnated laminar graphene structure are parallel to a primary surface of the anode current collector or the cathode current collector. In another preferred embodiment, the supercapacitor further comprises an anode current collector and/or a cathode current collector and the graphene sheets in the electrolyte-impregnated laminar graphene structure are perpendicular to a primary surface of the anode current collector or the cathode current collector.

In certain embodiments, the present invention provides a supercapacitor comprising an anode current collector, an anode, a cathode, a cathode current collector, an ion-permeable separator that electronically separates the anode and the cathode, and an electrolyte in ionic contact with the anode and the cathode, wherein the anode and/or the cathode contains an electrolyte-impregnated laminar graphene structure, which is composed of multiple graphene sheets being alternately spaced by thin electrolyte layers, from 0.4 nm to 10 nm in thickness (preferably <5 nm and more preferably <2 nm), and the multiple graphene sheets are substantially aligned along a desired direction, and wherein the laminar graphene structure has a physical density from 0.5 to 1.7 g/cm³ and a specific surface area from 50 to 3,300 m²/g, when measured in a dried state of the laminar graphene structure with the electrolyte removed.

If both the anode and the cathode contain such an electrode and the two electrodes have identical compositions, we have a symmetric supercapacitor. If the electrode contains only a graphene material or a graphene and a carbon or graphite material as the only electrode active material, we have an electric double layer capacitor (EDLC). The presently invented graphene supercapacitor electrode is capable of delivering a gravimetric specific capacitance of 150-350 F/g (based on the electric double layer capacitance alone), in contrast to the typical specific capacitance of 100-170 F/g of prior art graphene-based EDLC supercapacitors. Most significantly and surprisingly, the presently invented graphene supercapacitor electrode is capable of delivering a volumetric specific capacitance of 150-450 F/cm³ (based on EDLC mechanism alone), in contrast to the typical EDLC-based specific capacitance of 20-50 F/cm³ of prior art graphene-based EDLC supercapacitors (having a tap density typically from <0.1 to 0.3 g/cm³). These differences are huge and unexpected.

If at least an electrode contains a redox pair (e.g. graphene and an intrinsically conductive polymer or transition metal oxide), we have a redox or pseudo-capacitor. The supercapacitor is a lithium-ion capacitor or sodium-ion capacitor if the cathode contains the presently invented electrode (having graphene or graphene-carbon material mixture as the electrode active material) and the anode contains a pre-lithiated anode active material (e.g. pre-lithiated graphite or Si particles) or a pre-sodiated anode active material (e.g. pre-sodiated hard carbon particles).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1(A) A flow chart illustrating various prior art processes of producing exfoliated graphite products (graphite worms, flexible graphite foils and expanded graphite flakes), along with a process for producing graphene foam 40 a or graphene oxide foams 40 b;

FIG. 1(B) Schematic drawing illustrating the processes for producing conventional paper, mat, film, and membrane of simply aggregated graphite flakes or graphene platelets (NGPs). All processes begin with intercalation and/or oxidation treatment of graphitic materials (e.g. natural graphite particles).

FIG. 2 Schematic of a conventional activated carbon-based supercapacitor cell.

FIG. 3(A) Schematic drawing to illustrate an example of a compressing and consolidating operation (using a mold cavity cell equipped with a piston or ram) for forming a layer of highly compacted and oriented graphite flakes. Flakes of graphite worms or expanded graphite are aligned parallel to the bottom plane or perpendicular to the layer thickness direction.

FIG. 3(B) Schematic drawing to illustrate another example of a compressing and consolidating operation (using a mold cavity cell equipped with a piston or ram) for forming a layer of highly compacted and oriented graphite flakes. Graphite flakes are aligned perpendicular to the side plane (X-Y plane) or parallel to the layer thickness direction (Z direction).

FIG. 3(C) Schematic drawing to illustrate yet another example of a compressing and consolidating operation (using a mold cavity cell with a vacuum-assisted suction provision) for forming a layer of highly compacted and oriented graphite flakes. Graphite flakes are aligned parallel to the bottom plane or perpendicular to the layer thickness direction. Preferably, the resulting layer of electrolyte-impregnated laminar graphite flake structure is further compressed to achieve an even high tap density.

FIG. 3(D) A roll-to-roll process for producing a thick layer of electrolyte-impregnated laminar graphite structure. Graphite flakes are well-aligned on the supporting substrate plane.

FIG. 4 The electrode specific capacitance values of two series of supercapacitors (conventional and presently invented) plotted as a function of the electrode density.

FIG. 5 Ragone plots (gravimetric power density vs. energy density) of four symmetric supercapacitor (EDLC) cells containing activated and non-activated expanded graphite flakes (obtained from MCMBs) as the electrode active material and EMIMBF4 ionic liquid electrolyte. Two supercapacitors were prepared according to an embodiment of instant invention and, for comparison, the other two by the conventional slurry coating of electrodes.

FIG. 6 Ragone plots of two EDLC supercapacitors containing activated exfoliated graphite worms (obtained from chopped graphite fibers) that are oriented parallel and perpendicular, respectively, to the current collector surface plane.

FIG. 7 Ragone plots of two activated expanded graphite-conductive polymer redox supercapacitors (pseudo-capacitors) having activated expanded graphite/sulfonated polyaniline (S-PANi) redox pairs: one produced by the instant process (flakes oriented perpendicular to the current collector plane) and the other by the conventional process.

FIG. 8 Ragone plots of lithium ion capacitor (LIC) cells containing an anode of prelithiated graphite, activated exfoliated graphite worms as the cathode electrode active material and lithium salt-PC/DEC organic liquid electrolyte. Supercapacitors were prepared according to an embodiment of instant invention and by the conventional slurry coating of electrodes.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

As schematically illustrated in FIG. 2, a prior art supercapacitor cell is typically composed of an anode current collector 202 (e.g. Al foil 12-15 μm thick), an anode active material layer 204 (containing an anode active material, such as activated carbon particles 232 and conductive additives that are bonded by a resin binder, such as PVDF), a porous separator 230, a cathode active material layer 208 (containing a cathode active material, such as activated carbon particles 234, and conductive additives that are all bonded by a resin binder, not shown), a cathode current collector 206 (e.g. Al foil), and a liquid electrolyte disposed in both the anode active material layer 204 (also simply referred to as the “anode layer”) and the cathode active material layer 208 (or simply “cathode layer”). The entire cell is encased in a protective housing, such as a thin plastic-aluminum foil laminate-based envelop. The prior art supercapacitor cell is typically made by a process that includes the following steps:

-   -   a) The first step is mixing particles of the anode active         material (e.g. activated carbon), a conductive filler (e.g.         graphite flakes), a resin binder (e.g. PVDF) in a solvent (e.g.         NMP) to form an anode slurry. On a separate basis, particles of         the cathode active material (e.g. activated carbon), a         conductive filler (e.g. acetylene black), a resin binder (e.g.         PVDF) are mixed and dispersed in a solvent (e.g. NMP) to form a         cathode slurry.     -   b) The second step includes coating the anode slurry onto one or         both primary surfaces of an anode current collector (e.g. Cu or         Al foil), drying the coated layer by vaporizing the solvent         (e.g. NMP) to form a dried anode electrode coated on Cu or Al         foil. Similarly, the cathode slurry is coated and dried to form         a dried cathode electrode coated on Al foil.     -   c) The third step includes laminating an anode/Al foil sheet, a         porous separator layer, and a cathode/Al foil sheet together to         form a 3-layer or 5-layer assembly, which is cut and slit into         desired sizes and stacked to form a rectangular structure (as an         example of shape) or rolled into a cylindrical cell structure.     -   d) The rectangular or cylindrical laminated structure is then         encased in a laminated aluminum-plastic envelope or steel         casing.     -   e) A liquid electrolyte is then injected into the laminated         housing structure to make a supercapacitor cell.

There are several serious problems associated with this conventional process and the resulting supercapacitor cell:

-   -   1) It is very difficult to produce an electrode layer (anode         layer or cathode layer) that is thicker than 100 μm and         practically impossible or impractical to produce an electrode         layer thicker than 200 μm. There are several reasons why this is         the case. An electrode of 100 μm thickness typically requires a         heating zone of 30-50 meters long in a slurry coating facility,         which is too time consuming, too energy intensive, and not         cost-effective. A heating zone longer than 100 meters is not         unusual.     -   2) For some electrode active materials, such as graphene sheets,         it has not been possible to produce an electrode thicker than 50         m in a real manufacturing environment on a continuous basis.         This is despite the notion that some thicker electrodes have         been claimed in open or patent literature, which were prepared         in a laboratory on a small scale. In a laboratory setting,         presumably one could repeatedly add new materials to a layer and         manually consolidate the layer to increase the thickness of an         electrode. However, even with such a procedure, the resulting         electrode becomes very fragile and brittle. This is even worse         for graphene-based electrodes, since repeated compressions lead         to re-stacking of graphene sheets and, hence, significantly         reduced specific surface area and reduced specific capacitance.     -   3) With a conventional process, as depicted in FIG. 2, the         actual mass loadings of the electrodes and the apparent         densities for the active materials are too low. In most cases,         the active material mass loadings of the electrodes (areal         density) is significantly lower than 10 mg/cm² and the apparent         volume density or tap density of the active material is         typically less than 0.75 g/cm³ (more typically less than 0.5         g/cm³ and most typically less than 0.3 g/cm³) even for         relatively large particles of activated carbon. In addition,         there are so many other non-active materials (e.g. conductive         additive and resin binder) that add additional weights and         volumes to the electrode without contributing to the cell         capacity. These low areal densities and low volume densities         result in relatively low volumetric capacitances and low         volumetric energy density.     -   4) The conventional process requires dispersing electrode active         materials (anode active material and cathode active material) in         a liquid solvent (e.g. NMP) to make a wet slurry and, upon         coating on a current collector surface, the liquid solvent has         to be removed to dry the electrode layer. Once the anode and         cathode layers, along with a separator layer, are laminated         together and packaged in a housing to make a supercapacitor         cell, one then injects a liquid electrolyte into the cell. In         actuality, one makes the two electrodes wet, then makes the         electrodes dry, and finally makes them wet again. Such a         wet-dry-wet process is clearly not a good process at all.     -   5) Current supercapacitors (e.g. symmetric supercapacitors or         electric double layer capacitors, EDLC) still suffer from a         relatively low gravimetric energy density and low volumetric         energy density. Commercially available EDLCs exhibit a         gravimetric energy density of approximately 6 Wh/kg and no         experimental EDLC cells have been reported to exhibit an energy         density higher than 10 Wh/kg (based on the total cell weight) at         room temperature. Although experimental supercapacitors can         exhibit large volumetric electrode capacitances (50 to 100 F/cm³         in most cases) at the electrode level, their typical active mass         loading of <1 mg/cm², tap density of <0.1 g/cm³ and electrode         thicknesses of up to tens of micrometers in these experimental         cells remain significantly lower than those used in most         commercially available electrochemical capacitors, resulting in         energy storage devices with relatively low areal and volumetric         capacities and low volumetric energy densities based on the cell         (device) weight.     -   In literature, the energy density data reported based on either         the active material weight alone or electrode weight cannot         directly translate into the energy densities of a practical         supercapacitor cell or device. The “overhead weight” or weights         of other device components (binder, conductive additive, current         collectors, separator, electrolyte, and packaging) must also be         taken into account. The convention production process results in         an active material proportion being less than 30% by weight of         the total cell weight (<15% in some cases; e.g. for         graphene-based active material).

The present invention provides a process for producing a supercapacitor cell having a high electrode thickness (no theoretical limitation on the electrode thickness that can be made by using the present process), high active material mass loading, low overhead weight and volume, high volumetric capacitance, and high volumetric energy density. The electrode produced has been pre-impregnated with an electrolyte (aqueous, organic, ionic liquid, or polymer gel), wherein all graphite flakes have been wetted with a thin layer of electrolyte and all flakes have been well-aligned along one direction and closely packed together. The graphite flakes are alternatingly spaced with ultra-thin layers of electrolyte (0.4 nm to <10 nm, more typically <5 nm, most typically <2 nm). The process obviates the need to go through the lengthy and environmentally unfriendly wet-dry-wet procedures of the prior art process.

The present invention provides a process for producing an electrolyte-impregnated laminar graphite flake structure for use as a supercapacitor electrode. In a preferred embodiment, the process comprises: (a) preparing a graphite flake dispersion having multiple flakes of exfoliated graphite worms or expanded graphite dispersed in (or impregnated with) a liquid or gel electrolyte; and (b) subjecting the graphite flake dispersion to a forced assembly procedure, forcing the multiple graphite flakes to assemble into the electrolyte-impregnated laminar graphite structure, wherein the multiple graphite flakes are alternately spaced by thin electrolyte layers, less than 10 nm (preferably <5 nm) in thickness, and the multiple graphite flakes are substantially aligned along a desired direction, and wherein the laminar graphite flake structure has a physical density from 0.5 to 1.6 g/cm³ (more typically 0.7-1.3 g/cm³) and a specific surface area from 50 to 3,300 m²/g, when measured in a dried state of the laminar structure without the presence of electrolyte.

In some desired embodiments, the forced assembly procedure includes introducing a graphite flake dispersion, having an initial volume V₁, in a mold cavity cell and driving a piston into the mold cavity cell to reduce the graphite flake dispersion volume to a smaller value V₂, allowing excess electrolyte to flow out of the cavity cell (e.g. through holes of the mold cavity cell or of the piston) and aligning the multiple graphite flakes along a direction at an angle from 0° to 90° relative to a movement direction of said piston. It may be noted that the electrolyte used in this dispersion is the electrolyte for the intended supercapacitor.

FIG. 3(A) provides a schematic drawing to illustrate an example of a compressing and consolidating operation (using a mold cavity cell 302 equipped with a piston or ram 308) for forming a layer of highly compacted and oriented graphite flakes 314. Contained in the chamber (mold cavity cell 302) is a dispersion (e.g. suspension or slurry that is composed of expanded graphite flakes 304 randomly dispersed in a liquid or gel electrolyte 306). As the piston 308 is driven downward, the volume of the dispersion is decreased by forcing excess liquid electrolyte to flow through minute channels 312 on a mold wall or through small channels 310 of the piston. These small channels can be present in any or all walls of the mold cavity and the channel sizes can be designed to permit permeation of the electrolyte species, but not the solid graphite flakes (typically 0.5-10 m in length or width). The excess electrolyte is shown as 316 a and 316 b on the right diagram of FIG. 3(A). As a result of this compressing and consolidating operation, graphite flakes 314 are aligned parallel to the bottom plane or perpendicular to the layer thickness direction.

In this dispersion, practically each and every isolated graphite flake is surrounded by electrolyte species that are physically adsorbed on or chemically bonded to graphite flake surface. During the subsequent consolidating and aligning operation, isolated graphite flakes remain isolated or separated from one another through electrolyte. Upon removal of the excess electrolyte, graphite flakes remain spaced apart by electrolyte and this electrolyte-filled space can be as small as 0.4 nm. Contrary to the prior art teaching that the pores in activated carbon particles or between graphene sheets must be at least 2 nm in order to allow for the formation of electric double layers of charges in the electrolyte phase (but near the electrolyte-solid interface), we have discovered that the electrolyte spacer as small as 0.4 nm is capable of storing charges. Furthermore, since the electrolyte has been pre-loaded into the spaces between isolated graphite flakes, there is no electrolyte inaccessibility issue in the presently invented supercapacitor. The present invention has essentially overcome all the significant, longstanding shortcomings of using exfoliated graphite worms, expanded graphite flakes, or even graphene as a supercapacitor electrode active material.

Shown in FIG. 3(B) is a schematic drawing to illustrate another example of a compressing and consolidating operation (using a mold cavity cell equipped with a piston or ram) for forming a layer of highly compacted and oriented graphite flakes 320. The piston is driven downward along the Y-direction. The graphite flakes are aligned on the X-Z plane and perpendicular to X-Y plane (along the Z- or thickness direction). This layer of oriented graphite flakes can be attached to a current collector (e.g. Al foil) that is basically represented by the X-Y plane. In the resulting electrode, graphite flakes are aligned perpendicular to the current collector. Such an orientation is conducive to a faster charge response and, hence, leads to a higher power density as compared to the corresponding electrode featuring graphite flakes being aligned parallel to the current collector plane.

FIG. 3(C) provides a schematic drawing to illustrate yet another example of a compressing and consolidating operation (using a mold cavity cell with a vacuum-assisted suction provision) for forming a layer of highly compacted and oriented graphite flakes 326. The process begins with dispersing isolated graphite flakes 322 and an optional conductive filler in a liquid or gel electrolyte 324 to form a dispersion. This is followed by generating a negative pressure via a vacuum system that sucks excess electrolyte 332 through channels 330. This compressing and consolidating operation acts to reduce the dispersion volume and align all the isolated graphite flakes on the bottom plane of a mold cavity cell. Compacted graphite flakes are aligned parallel to the bottom plane or perpendicular to the layer thickness direction. Preferably, the resulting layer of electrolyte-impregnated laminar graphite flake structure is further compressed to achieve an even high tap density.

Thus, in some desired embodiments, the forced assembly procedure includes introducing dispersion of graphite flakes (activated or un-activated) in a mold cavity cell having an initial volume V₁, and applying a suction pressure through a porous wall of the mold cavity to reduce the graphite dispersion volume to a smaller value V₂, allowing excess electrolyte to flow out of the cavity cell through the porous wall and aligning the multiple graphite flakes along a direction at an angle from approximately 0° to approximately 90° relative to a suction pressure direction; this angle depending upon the inclination of the bottom plane with respect to the suction direction.

FIG. 3(D) shows a roll-to-roll process for producing a thick layer of electrolyte-impregnated laminar graphite flake structure. This process begins by feeding a continuous solid substrate 332 (e.g. PET film or stainless steel sheet) from a feeder roller 331. A dispenser 334 is operated to dispense dispersion 336 of isolated graphite flakes and electrolyte onto the substrate surface to form a layer of deposited dispersion 338, which feeds through the gap between two compressing rollers, 340 a and 340 b, to form a layer of electrolyte-impregnated, highly oriented graphite flakes. The graphite flakes are well-aligned on the supporting substrate plane. If so desired, a second dispenser 344 is then operated to dispense another layer of dispersion 348 on the surface of the previously consolidated dispersion layer. The two-layer structure is then driven to pass through the gap between two roll-pressing rollers 350 a and 350 b to form a thicker layer 352 of electrolyte-impregnated laminar graphite flake structure, which is taken up by a winding roller 354.

Thus, in some preferred embodiments, the forced assembly procedure includes introducing a first layer of the graphite flake dispersion onto a surface of a supporting conveyor and driving the layer of graphite flake suspension supported on the conveyor through at least a pair of pressing rollers to reduce the thickness of the graphite dispersion layer and align the multiple graphite flakes along a direction parallel to the conveyor surface for forming a layer of electrolyte-impregnated laminar graphite structure.

The process may further include a step of introducing a second layer of the graphite dispersion onto a surface of the layer of electrolyte-impregnated laminar structure to form a two layer laminar structure, and driving the two-layer laminar structure through at least a pair of pressing rollers to reduce a thickness of the second layer of graphite flake dispersion and align the multiple graphite flakes along a direction parallel to the conveyor surface for forming a layer of electrolyte-impregnated laminar structure. The same procedure may be repeated by allowing the conveyor to move toward a third set of pressing rollers, depositing additional (third) layer of graphite flake dispersion onto the two-layer structure, and forcing the resulting 3-layer structure to go through the gap between the two rollers in the third set to form a further compacted, electrolyte-impregnated laminar graphite flake structure.

The above paragraphs about FIG. 3(A) to FIG. 3(D) are but four of the many examples of possibly apparatus or processes that can be used to produce electrolyte-impregnated laminar graphite flake strictures that contain highly oriented and closely packed graphite flakes spaced by thin layers of electrolyte.

Exfoliated graphite may be obtained by immersing powders or filaments of a starting graphitic material (e.g. natural graphite powder) in an oxidizing liquid medium (e.g. a mixture of sulfuric acid, nitric acid, and potassium permanganate) in a reaction vessel at a desired temperature for a period of time (typically from 0.5 to 96 hours, depending upon the nature of the starting material and the type of oxidizing agent used). The resulting graphite oxide particles (sulfuric acid-intercalated graphite or graphite intercalation compound, GIC) may then be subjected to thermal exfoliation to produce exfoliated graphite worms. Graphite worms are composed of exfoliated graphite flakes that remain weakly interconnected. Graphite worms may be broken up by using mechanical shearing, air jet milling, ultrasonication, etc.

The aforementioned features are further described and explained in detail as follows: As illustrated in FIG. 1(B), a graphite particle (e.g. 100) is typically composed of multiple graphite crystallites or grains. A graphite crystallite is made up of layer planes of hexagonal networks of carbon atoms. These layer planes of hexagonally arranged carbon atoms are substantially flat and are oriented or ordered so as to be substantially parallel and equidistant to one another in a particular crystallite. These layers of hexagonal-structured carbon atoms, commonly referred to as graphene layers or basal planes, are weakly bonded together in their thickness direction (crystallographic c-axis direction) by weak van der Waals forces and groups of these graphene layers are arranged in crystallites. The graphite crystallite structure is usually characterized in terms of two axes or directions: the c-axis direction and the a-axis (or b-axis) direction. The c-axis is the direction perpendicular to the basal planes. The a- or b-axes are the directions parallel to the basal planes (perpendicular to the c-axis direction).

A highly ordered graphite particle can consist of crystallites of a considerable size, having a length of L_(a) along the crystallographic a-axis direction, a width of L_(b) along the crystallographic b-axis direction, and a thickness L_(c) along the crystallographic c-axis direction. The constituent graphene planes of a crystallite are highly aligned or oriented with respect to each other and, hence, these anisotropic structures give rise to many properties that are highly directional. For instance, the thermal and electrical conductivity of a crystallite are of great magnitude along the plane directions (a- or b-axis directions), but relatively low in the perpendicular direction (c-axis). As illustrated in the upper-left portion of FIG. 1(B), different crystallites in a graphite particle are typically oriented in different directions and, hence, a particular property of a multi-crystallite graphite particle is the directional average value of all the constituent crystallites.

Due to the weak van der Waals forces holding the parallel graphene layers, natural graphite can be treated so that the spacing between the graphene layers can be appreciably opened up so as to provide a marked expansion in the c-axis direction, and thus form an expanded graphite structure in which the laminar character of the carbon layers is substantially retained. The process for manufacturing flexible graphite is well-known in the art. In general, flakes of natural graphite (e.g. 100 in FIG. 1(B)) are intercalated in an acid solution to produce graphite intercalation compounds (GICs, 102). The GICs are washed, dried, and then exfoliated by exposure to a high temperature for a short period of time. This causes the flakes to expand or exfoliate in the c-axis direction of the graphite up to 80-300 times of their original dimensions. The exfoliated graphite flakes are vermiform in appearance and, hence, are commonly referred to as graphite worms 104.

These worms of graphite flakes which have been greatly expanded can be formed without the use of a binder into cohesive or integrated sheets of expanded graphite, e.g. webs, papers, strips, tapes, foils, mats or the like (typically referred to as “flexible graphite” 106) having a typical density of about 0.04-2.0 g/cm³ for most applications.

The upper left portion of FIG. 1(A) shows a flow chart that illustrates the prior art processes used to fabricate flexible graphite foils. The processes typically begin with intercalating graphite particles 20 (e.g., natural graphite or synthetic graphite) with an intercalant (typically a strong acid or acid mixture) to obtain a graphite intercalation compound 22 (GIC). After rinsing in water to remove excess acid, the GIC becomes “expandable graphite.” The GIC or expandable graphite is then exposed to a high temperature environment (e.g., in a tube furnace preset at a temperature in the range of 800-1,050° C.) for a short duration of time (typically from 15 seconds to 2 minutes). This thermal treatment allows the graphite to expand in its c-axis direction by a factor of 30 to several hundreds to obtain a worm-like vermicular structure 24 (graphite worm), which contains exfoliated, but un-separated graphite flakes with large pores interposed between these interconnected flakes.

In one prior art process, the exfoliated graphite (or mass of graphite worms) is re-compressed by using a calendaring or roll-pressing technique to obtain flexible graphite foils (26 in FIG. 1(A) or 106 in FIG. 1(B)), which are typically 100-300 m thick. In another prior art process, the exfoliated graphite worm 24 may be impregnated with a resin and then compressed and cured to form a flexible graphite composite, which is normally of low strength as well. In addition, upon resin impregnation, the electrical and thermal conductivity of the graphite worms could be reduced by two orders of magnitude.

Alternatively, the exfoliated graphite may be subjected to high-intensity mechanical shearing/separation treatments using a high-intensity air jet mill, high-intensity ball mill, or ultrasonic device to produce separated nano graphene platelets 33 (NGPs) with all the graphene platelets thinner than 100 nm, mostly thinner than 10 nm, and, in many cases, being single-layer graphene (also illustrated as 112 in FIG. 1(B)). An NGP is composed of a graphene sheet or a plurality of graphene sheets with each sheet being a two-dimensional, hexagonal structure of carbon atoms. A mass of multiple NGPs (including discrete sheets/platelets of single-layer and/or few-layer graphene or graphene oxide, 33 in FIG. 1(A)) may be made into a graphene film/paper (34 in FIG. 1(A) or 114 in FIG. 1(B)) using a film- or paper-making process.

Further alternatively, with a low-intensity shearing, graphite worms tend to be separated into the so-called expanded graphite flakes (108 in FIG. 1(B) having a thickness >100 nm. These flakes can be formed into graphite paper or mat 106 using a paper- or mat-making process. This expanded graphite paper or mat 106 is just a simple aggregate or stack of discrete flakes having defects, interruptions, and mis-orientations between these discrete flakes.

The exfoliated graphite worms or expanded graphite flakes may be further subjected to the following treatments, separately or in combination, prior to being dispersed in an electrolyte or impregnated by an electrolyte:

-   -   (a) Activation treatment (analogous to activation of carbon         black materials) may be used to create additional surfaces and         possibly imparting functional chemical groups to these surfaces.         The activation treatment can be accomplished through CO₂         physical activation, KOH chemical activation, or exposure to         nitric acid, fluorine, or ammonia plasma.     -   (b) Chemically functionalizing or doping with atomic, ionic, or         molecular species can be carried out. Useful surface functional         groups may include quinone, hydroquinone, quaternized aromatic         amines, mercaptans, or disulfides. This class of functional         groups can impart pseudo-capacitance to graphene-based         supercapacitors.     -   (c) Coating or grafting with an intrinsically conductive polymer         (conducting polymers, such as polyacetylene, polypyrrole,         polyaniline, polythiophene, and their derivatives, are good         choices for use in the present invention) can further increasing         the capacitance value through pseudo-capacitance effects such as         redox reactions.     -   (d) Deposition with transition metal oxides or sulfides, such as         RuO₂, TiO₂, MnO₂, Cr₂O₃, and Co₂O₃, for the purpose of forming         redox pairs with graphene sheets, can impart pseudo-capacitance         to the electrode.

In the physical activation treatment, flakes of exfoliated graphite worms or expanded graphite are activated using hot gases. These flakes are oxidizing atmospheres (oxygen or steam) at temperatures above 250° C., usually in the temperature range of 600-1200° C.

In the chemical activation treatment, flakes of exfoliated graphite worms or expanded graphite are impregnated with certain chemicals. The chemical is typically an acid, strong base, or a salt (phosphoric acid, potassium hydroxide, sodium hydroxide, calcium chloride, and zinc chloride). Then, these flakes are treated at a temperature range of 450−900° C. Chemical activation is preferred over physical activation owing to the lower temperatures and shorter time needed for activating material.

In the instant invention, there is no limitation on the type of liquid or gel electrolytes that can be used in the supercapacitor: aqueous, organic, gel, and ionic liquid. Typically, electrolytes for supercapacitors consist of solvent and dissolved chemicals (e.g. salts) that dissociate into positive ions (cations) and negative ions (anions), making the electrolyte electrically conductive. The more ions the electrolyte contains, the better its conductivity, which also influences the capacitance. In supercapacitors, the electrolyte provides the molecules for the separating monolayer in the Helmholtz double-layer (electric double layer) and delivers the ions for pseudocapacitance.

Water is a relatively good solvent for dissolving inorganic chemicals. When added together with acids such as sulfuric acid (H₂SO₄), alkalis such as potassium hydroxide (KOH), or salts such as quaternary phosphonium salts, sodium perchlorate (NaClO₄), lithium perchlorate (LiClO₄) or lithium hexafluoride arsenate (LiAsF₆), water offers relatively high conductivity values. Aqueous electrolytes have a dissociation voltage of 1.15 V per electrode and a relatively low operating temperature range. Water electrolyte-based supercapacitors exhibit low energy density.

Alternatively, electrolytes may contain organic solvents, such as acetonitrile, propylene carbonate, tetrahydrofuran, diethyl carbonate, γ-butyrolactone, and solutes with quaternary ammonium salts or alkyl ammonium salts such as tetraethylammonium tetrafluoroborate (N(Et)₄BF₄) or triethyl (methyl) tetrafluoroborate (NMe(Et)₃BF₄). Organic electrolytes are more expensive than aqueous electrolytes, but they have a higher dissociation voltage of typically 1.35 V per electrode (2.7 V capacitor voltage), and a higher temperature range. The lower electrical conductivity of organic solvents (10 to 60 mS/cm) leads to a lower power density, but a higher energy density since the energy density is proportional to the square of the voltage.

The ionic liquid is composed of ions only. Ionic liquids are low melting temperature salts that are in a molten or liquid state when above a desired temperature. For instance, a salt is considered as an ionic liquid if its melting point is below 100° C. If the melting temperature is equal to or lower than room temperature (25° C.), the salt is referred to as a room temperature ionic liquid (RTIL). The IL salts are characterized by weak interactions, due to the combination of a large cation and a charge-delocalized anion. This results in a low tendency to crystallize due to flexibility (anion) and asymmetry (cation).

A typical and well-known ionic liquid is formed by the combination of a 1-ethyl-3-methylimidazolium (EMI) cation and an N,N-bis(trifluoromethane)sulphonamide (TFSI) anion. This combination gives a fluid with an ionic conductivity comparable to many organic electrolyte solutions and a low decomposition propensity and low vapor pressure up to ˜300-400° C. This implies a generally low volatility and non-flammability and, hence, a much safer electrolyte for batteries.

Ionic liquids are basically composed of organic ions that come in an essentially unlimited number of structural variations owing to the preparation ease of a large variety of their components. Thus, various kinds of salts can be used to design the ionic liquid that has the desired properties for a given application. These include, among others, imidazolium, pyrrolidinium and quaternary ammonium salts as cations and bis(trifluoromethanesulphonyl) imide, bis(fluorosulphonyl)imide, and hexafluorophosphate as anions. Based on their compositions, ionic liquids come in different classes that basically include aprotic, protic and zwitterionic types, each one suitable for a specific application.

Common cations of room temperature ionic liquids (RTILs) include, but not limited to, tetraalkylammonium, di-, tri-, and tetra-alkylimidazolium, alkylpyridinium, dialkyl-pyrrolidinium, dialkylpiperidinium, tetraalkylphosphonium, and trialkylsulfonium. Common anions of RTILs include, but not limited to, BF₄ ⁻, B(CN)₄ ⁻, CH₃BF₃ ⁻, CH₂CHBF₃ ⁻, CF₃BF₃ ⁻, C₂F₅BF₃ ⁻, n-C₃F₇BF₃ ⁻, n-C₄F₉BF₃ ⁻, PF₆ ⁻, CF₃CO₂ ⁻, CF₃SO₃—, N(SO₂CF₃)₂ ⁻, N(COCF₃)(SO₂CF₃)⁻, N(SO₂F)₂ ⁻, N(CN)₂ ⁻, C(CN)₃ ⁻, SCN⁻, SeCN⁻, CuCl₂ ⁻, AlCl₄ ⁻, F(HF)_(2.3) ⁻, etc. Relatively speaking, the combination of imidazolium- or sulfonium-based cations and complex halide anions such as AlCl₄ ⁻, BF₄ ⁻, CF₃CO₂ ⁻, CF₃SO₃ ⁻, NTf₂ ⁻, N(SO₂F)₂ ⁻, or F(HF)_(2.3) ⁻ results in RTILs with good working conductivities.

RTILs can possess archetypical properties such as high intrinsic ionic conductivity, high thermal stability, low volatility, low (practically zero) vapor pressure, non-flammability, the ability to remain liquid at a wide range of temperatures above and below room temperature, high polarity, high viscosity, and wide electrochemical windows. These properties, except for the high viscosity, are desirable attributes when it comes to using an RTIL as an electrolyte ingredient (a salt and/or a solvent) in a supercapacitor.

In order to make a pseudo-capacitor (a supercapacitor that works on the development of pseudo-capacitance through redox pair formation), the anode active material or cathode active material may be designed to contain graphite flakes (activated or un-activated) and a redox pair partner material selected from a metal oxide, a conducting polymer (e.g. conjugate-chain polymers), a non-conducting polymer (e.g. polyacrylonitrile, PAN), an organic material (e.g. hydroquinone), a carbon material, an inorganic material, or a combination thereof. Many of the materials that can pair up with graphite flakes are well-known in the art.

For instance, the metal oxide or inorganic materials that serve in such a role include RuO₂, IrO₂, NiO, MnO₂, VO₂, V₂O₅, V₃O₈, TiO₂, Cr₂O₃, Co₂O₃, Co₃O₄, PbO₂, Ag₂O, MoC_(x), Mo₂N, or a combination thereof. In general, the inorganic material may be selected from a metal carbide, metal nitride, metal boride, metal dichalcogenide, or a combination thereof. Preferably, the desired metal oxide or inorganic material is selected from an oxide, dichalcogenide, trichalcogenide, sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, iron, or nickel in a nanowire, nano-disc, nano-ribbon, or nano platelet form. These materials or their precursors can be incorporated in the coating slurry prior to the coating or film forming procedure. Alternatively, their molecular precursors in a liquid solution may be impregnated into the pores of the graphite foam and the precursor is then thermally or chemically converted into the desired inorganic species (e.g. transition metal oxide). The liquid or gel electrolyte is then impregnated into the foam.

The following examples are used to illustrate some specific details about the best modes of practicing the instant invention and should not be construed as limiting the scope of the invention.

Example 1: Preparation of Exfoliated Graphite Worms and Expanded Graphite Flakes from Meso-Carbon Micro-Beads (MCMBs)

Meso-carbon microbeads (MCMBs) were supplied from China Steel Chemical Co., Kaohsiung, Taiwan. This material has a density of about 2.24 g/cm³ with a median particle size of about 16 μm. MCMB (10 grams) were intercalated with an acid solution (sulfuric acid, nitric acid, and potassium permanganate at a ratio of 4:1:0.05) for a period of time from 4 hours up to 48 hours. Upon completion of the reaction, the mixture was poured into deionized water and filtered. The intercalated MCMBs were repeatedly washed in a 5% solution of HCl to remove most of the sulphate ions. The sample was then washed repeatedly with deionized water until the pH of the filtrate was no less than 4.0. The slurry was then dried in a vacuum for 24 hours to obtain a graphite intercalation compound (GIC).

The GIC was then thermally exfoliated at 650° C. for 1 minute to produce exfoliated graphite worms, which were divided into two portions. One portion was subjected to chemical activation by mixing the graphite worms with KOH at a 1:1 weight ratio and then heated the mixture to 800° C. for 2 hours to produce activated graphite worms, having a specific surface area of 1,775 m²/g. The other portion, having a specific surface area of 344 m²/g, was used as a control sample. The graphite worms, with or without chemical activation, were then made into supercapacitor electrodes and supercapacitor cells using both the presently invented processes (as illustrated in FIG. 3(C)) and the conventional production process (preparation of NMP/exfoliated graphite slurry, coating, drying, cell lamination, and electrolyte injection).

Example 2: Preparation of Exfoliated Graphite Worms and Expanded Graphite Flakes from Short Graphite Fibers

Chopped graphite fibers with an average diameter of 12 μm and natural graphite particles were separately used as a starting material, which was immersed in a mixture of concentrated sulfuric acid, nitric acid, and potassium permanganate (as the chemical intercalate and oxidizer) to prepare graphite intercalation compounds (GICs). The starting material was first dried in a vacuum oven for 24 h at 80° C. Then, a mixture of concentrated sulfuric acid, fuming nitric acid, and potassium permanganate (at a weight ratio of 4:1:0.05) was slowly added, under appropriate cooling and stirring, to a three-neck flask containing fiber segments. After 4 hours of reaction, the acid-treated graphite fibers or natural graphite particles were filtered and washed thoroughly with deionized water until the pH level of the solution reached 6. After drying the product at 100° C. overnight, we obtained a graphite intercalation compound (GIC) or graphite oxide fiber.

The GIC was then submitted to a thermal exfoliation treatment at 800° C. for 45 seconds to obtain exfoliated graphite worms. Some of these worms were submitted to low-intensity shearing using a kitchen-scale food processor to produce expanded graphite flakes.

Part of the expanded graphite flakes was mixed with NMP to form a slurry, which was then coated onto both primary surfaces of a sheet of Al foil (serving as a current collector). The maximum thickness of expanded graphite flake layer coated on each side of Al foil was approximately 85 μm, beyond which the electrode layer has the tendency to get cracked or delaminated when NMP was removed. Two pieces of electrodes, each with Al foil coated with expanded graphite (+5% acetylene black and 7% PVDF binder resin), spaced by a porous separator, were laminated to form a supercapacitor cell. The cell was enclosed in a nylon-Al laminated housing (envelop), injected with a liquid electrolyte, and then sealed. This is a conventional symmetric EDLC supercapacitor.

The remaining portion of the expanded graphite flakes was dispersed in the same liquid electrolyte to form a dispersion. Part of the dispersion was compressed and consolidated into a layer of electrolyte-impregnated, compacted and highly oriented graphite flakes (electrolyte-impregnated laminar graphite flake structure) according to the process illustrated in FIG. 3(A). This was bonded to a current collector (Al foil) with the graphene sheets aligned parallel to the Al foil plane. Other part of the dispersion was made into a layer of electrolyte-impregnated laminar structure having graphite flakes aligned perpendicular to the current collector plane, as illustrated in FIG. 3(B).

Example 3: Preparation of Exfoliated Graphite Worms and Electrodes from Natural Graphite

Graphite intercalation compound or graphite oxide was prepared by oxidation of natural flake graphite with an oxidizer liquid consisting of sulfuric acid, sodium nitrate, and potassium permanganate at a ratio of 4:1:0.05 at 30° C. When natural graphite flakes (particle sizes of 25 m) were immersed and dispersed in the oxidizer mixture liquid for 4 hours, the suspension or slurry remains optically opaque and dark. After this, the reacting mass was rinsed with water 3 times to adjust the pH value to at least 3.0. The mass was then dried in a vacuum oven at 80° C. for 24 hours to obtain a GIC. The GIC was thermally exfoliated at 900° C. for 60 seconds to obtain exfoliated graphite worms. Some of the worms were subjected to low-intensity shearing using a food processor to obtain expanded graphite flakes. Some amount of the worms and some amount of the expanded graphite flakes were subjected to chemical activation (using NaOH melt at 800° C. for 6 hours) to obtain activated graphite worms and activated expanded graphite flakes, respectively.

Some of these graphite flakes (activated or non-activated) and some of these graphite worms (activated or non-activated) were then dispersed in an electrolyte to form several dispersion samples, which were then made into supercapacitor electrodes using the presently invented process (roll-pressing-based as illustrated in FIG. 3(C)). Some were made into conventional supercapacitors using the prior art slurry coating approach.

Example 4: Preparation of Intrinsically Conductive Polymer-Graphene Redox Pairs

In this series of examples, intrinsically conductive polymers (e.g. polyaniline, poly polypyrrole, and polythiophene) and their sulfonated versions are evaluated for their effectiveness as a redox pair partner material with a graphite flake material.

The chemical synthesis of the sulfonated polyaniline (S-PANi) was accomplished by reacting polyaniline with concentrated sulfuric acid. The procedure was similar to that used by Epstein, et al. (U.S. Pat. No. 5,109,070, Apr. 28, 1992). The resulting S-PANi can be represented by the following Formula 1, with R₁, R₂, R₃, and R₄ group being H, SO₃ ⁻ or SO₃H (R₅═H) with the content of the latter two being varied between 30% and 75% (i.e., the degree of sulfonation varied between 30% and 75%).

The electron conductivity of these SO₃ ⁻ or SO₃H-based S-PANi compositions was in the range of 0.1 S/cm to 0.5 S/cm when the degree of sulfonation was from approximately 30% to 75% (with y being approximately 0.4-0.6). The S-PANi/water solution was mixed with expanded graphite flake (EGF)/water solution at a S-PANi/EGF weight ratio of ⅕-½ and, upon water removal, the S-PANi was precipitated out and coated onto the EGF surfaces for forming a redox pair. The polymer-coated EGF was then dispersed in electrolyte and made into pseudo-capacitance electrodes using both the presently invented process and the conventional process.

A sulfonated pyrrole-based polymer (with X=NH and Y=SO₃ ⁻, m=1, and A=H in the following formula) was synthesized by following a procedure adapted from Aldissi, et al., U.S. Pat. No. 4,880,508, Nov. 14, 1989.

For solution impregnation, as one example, approximately 5.78 g of the resulting sulfonated polypyrrole was dissolved in 100 ml of distilled water. Then, the aqueous solution was mixed with EGF/water solution and the resulting liquid mixture was dried to allow for precipitation and deposition of sulfonated polypyrrole onto surfaces of expanded graphite flakes to form a redox pair. Conductive polymer-coated expanded graphite flakes were then dispersed in a liquid electrolyte and made into pseudo-capacitance electrodes using both the presently invented process and the conventional process.

Water-soluble conductive polymers having a thiophene ring (X=sulfur) and alkyl groups containing 4 carbon atoms (m=4) in the above Formula 2 were prepared, according to a method adapted from Aldissi, et al. (U.S. Pat. No. 4,880,508, Nov. 14, 1989). The surfactant molecules of these polymers were sulfonate groups with sodium. Conductivity of this polymer in a self-doped state was found to be from about 10⁻³ to about 10⁻² S/cm.

A doped poly (alkyl thiophene) (PAT) with Y=SO₃H and A=H in Formula 2 that exhibited an electron conductivity of 12.5 S/cm was dissolved in an aqueous hydrogen peroxide (H₂O2) solution. The resulting polymer solution was mixed with an EGF/water solution and dried to form a redox pair. Conductive polymer-coated expanded graphite flakes were then dispersed in a liquid electrolyte and made into pseudo-capacitance electrodes using both the presently invented process and the conventional process.

We have surprisingly discovered that the sulfonated conductive polymer (e.g. S-PANi), paired up with an EGF material and prepared with the presently invented compressing and consolidating approach, leads to a significantly higher pseudo-capacitance value when compared with the corresponding material prepared by the conventional approach; e.g. 742 F/g vs. 554 (S-PANi); 645 F/cm³ vs. 343 F/cm³ (S-PPy); and 542 F/g vs. 312 F/g (S-PAT).

Example 5: Preparation of MnO₂-Expanded Graphite Flake Redox Pairs

The MnO₂ powder was synthesized in the presence of expanded graphite flakes (EGF). In this method, a 0.1 mol/L KMnO₄ aqueous solution was prepared by dissolving potassium permanganate in deionized water. Meanwhile 13.3 g surfactant of high purity sodium bis(2-ethylhexyl) sulfosuccinate was added in 300 mL iso-octane (oil) and stirred well to obtain an optically transparent solution. Then, 32.4 mL of 0.1 mol/L KMnO₄ solution were added in the solution, which was followed by dispersing pristine EGF in the solution. The resulting suspension was ultrasonicated for 30 min and a dark brown precipitate of MnO₂ was coated on surfaces of EGF. The products were recovered, washed several times with distilled water and ethanol, and dried at 80° C. for 12 h. The samples were MnO₂-coated EGF, which were re-dispersed into a liquid electrolyte to form a dispersion. This EGF-electrolyte dispersion was then consolidated into an electrolyte-impregnated laminar graphite structure using the vacuum-assisted method (FIG. 3(C)). In such a structure, EGF and MnO₂ form a redox pair operating to produce pseudo-capacitance in a supercapacitor. For comparison, a corresponding supercapacitor was made using conventional slurry coating, drying, packaging, and electrolyte injection. Even with the presence of MnO₂ phase coated on graphite flake surfaces, the presently invented method is capable of closely packing and highly orienting the coated graphite flakes into an electrode of a high tap density with thin electrolyte layers inter-spaced between coated graphite flakes. The specific capacitance values of the resulting supercapacitor are 411 F/g and 520 F/cm³, which are significantly higher than the 288 F/g and 214 F/cm³ of its conventional counterpart prepared by the conventional procedures of combined slurry coating, drying, laminating, and electrolyte injection. The differences are quite dramatic and unexpected.

Example 6: Details about Evaluation of Various Supercapacitor Cells

In most of the examples investigated, both the inventive supercapacitor cells and their conventional counterparts were fabricated and evaluated. The latter cells, for comparison purposes, were prepared by the conventional procedures of slurry coating of electrodes, drying of electrodes, assembling of anode layer, separator, and cathode layer, packaging of assembled laminate, and injection of liquid electrolyte. In a conventional cell, an electrode (cathode or anode), is typically composed of 85% an electrode active material (e.g. activated carbon, inorganic nanodiscs, etc.), 5% Super-P (acetylene black-based conductive additive), and 10% PTFE, which were mixed and coated on Al foil. The thickness of electrode is around 100 μm. For each sample, both coin-size and pouch cells were assembled in a glove box. The capacity was measured with galvanostatic experiments using an Arbin SCTS electrochemical testing instrument. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were conducted on an electrochemical workstation (CHI 660 System, USA).

Galvanostatic charge/discharge tests were conducted on the samples to evaluate the electrochemical performance. For the galvanostatic tests, the specific capacity (q) is calculated as q=I*t/m  (1) where I is the constant current in mA, t is the time in hours, and m is the cathode active material mass in grams. With voltage V, the specific energy (E) is calculated as, E=∫Vdq  (2) The specific power (P) can be calculated as P=(E/t)(W/kg)  (3) where t is the total charge or discharge step time in hours. The specific capacitance (C) of the cell is represented by the slope at each point of the voltage vs. specific capacity plot, C=dq/dV  (4) For each sample, several current density (representing charge/discharge rates) were imposed to determine the electrochemical responses, allowing for calculations of energy density and power density values required of the construction of a Ragone plot (power density vs. energy density).

Example 7: Achievable Electrode Tap Density and its Effect on Electrochemical Performance of Supercapacitor Cells

The presently invented process allows us to prepare a graphite flake electrode of any practical tap density from 0.1 to 1.6 g/cm³. It may be noted that the graphite flake-based supercapacitor electrodes prepared by conventional processes are limited to <0.3 and mostly <0.2 g/cm³. Furthermore, as discussed earlier, only thinner electrodes can be prepared using these conventional processes. As a point of reference, the activated carbon-based electrode exhibits a tap density typically from 0.3 to 0.5 g/cm³.

A series of EDLC electrodes with different tap densities were prepared from the same batch of electrolyte-impregnated graphite flake laminar structures, but roll-pressed to different extents. The volume and weights of an electrode were measured before and after electrolyte removal and before and after roll-pressing. These measurements enabled us to estimate the tap density of the dried electrode (wet electrode volume/weight minus the amount of electrolyte actually absorbed). For comparison purposes, graphite flake-based electrodes of comparable thickness (70-75 μm) were also prepared using the conventional slurry coating process (the wet-dry-wet procedures). The electrode specific capacitance values of these supercapacitors using an organic electrolyte (acetonitrile) are summarized in FIG. 4. There are several significant observations that can be made from these data:

-   -   (A) Given comparable electrode thickness, the presently invented         activated graphite flake-based supercapacitors exhibit         significantly higher gravimetric specific capacitance (152-239         F/g) as compared to those (128-145 F/g) of the corresponding         graphene-based electrodes prepared by the conventional process,         all based on EDLC alone.     -   (B) The highest achievable tap density of the electrode prepared         by the conventional method is 0.15-0.30 g/cm³. In contrast, the         presently invented process makes it possible to achieve a tap         density of 0.37-1.62 g/cm3 (based on this series of samples         alone); these unprecedented values even surpass those (0.3-0.5         g/cm³) of activated carbon electrodes by a large margin.     -   (C) The presently invented graphite flake electrodes exhibit a         volumetric specific capacitance up to 265 F/cm³, which is also         an unprecedented value. In contrast, the graphite flake         electrodes prepared according to the conventional method shows a         specific capacitance in the range of 22-39 F/cm³; the         differences are dramatic.

Shown in FIG. 5 are Ragone plots (gravimetric power density vs. energy density) of four symmetric supercapacitor (EDLC) cells containing activated and non-activated expanded graphite flakes (obtained from MCMBs) as the electrode active material and EMIMBF4 ionic liquid electrolyte. Two supercapacitors were prepared according to an embodiment of instant invention and, for comparison, two by the conventional slurry coating of electrodes. Several significant observations can be made from these data:

-   -   (A) Both the gravimetric energy densities and power densities of         the supercapacitor cells prepared by the presently invented         method are significantly higher than those of their counterparts         prepared via the conventional method. The differences are highly         dramatic. The presently invented approach enables the production         of significantly thicker electrodes and orientation of expanded         graphite flakes that is conducive to fast ion migration and         formation of electric double layers. The inventive method is         also more capable of effectively packing graphite flakes         together without graphite flake re-stacking (due to         pre-impregnated electrolyte serving as a spacer) and without         forming any dry spots (having no spaces not accessible to liquid         electrolyte).     -   (B) Activation of expanded graphite flakes led to significantly         higher specific capacitance likely dues to the significantly         higher specific surface area. With or without activation,         expanded graphite flakes provide much higher specific         capacitance if they are properly oriented.

FIG. 6 shows the Ragone plots of two EDLC supercapacitors containing activated exfoliated graphite worms (obtained from chopped graphite fibers) that are oriented parallel and perpendicular, respectively, to the current collector surface plane. It is clear that, when the constituent graphite flakes of worms are oriented perpendicular to the current collector plane (i.e. parallel to the ion movement direction), the resulting electrodes can store larger amounts of charges and deliver higher power. The maximum energy density, 16.1 Wh/kg), is 2.5 times higher as compared to those of current commercial supercapacitors. The maximum power density, 14,521 W/kg, is approximately 2 times that of commercial supercapacitor cells.

FIG. 7 shows the Ragone plots of two activated expanded graphite-conductive polymer redox supercapacitors (pseudo-capacitors) having activated expanded graphite/sulfonated polyaniline (S-PANi) redox pairs: one produced by the instant process (flakes oriented perpendicular to the current collector plane) and the other by the conventional process. Both contain Na₂SO₄ aqueous electrolyte. Quite unexpectedly, sulfonated conductive polymers, when paired up with properly oriented activated expanded graphite flakes, lead to a supercapacitor exhibiting an exceptionally high energy density and high power density. Both the energy density and power density are significantly higher than those of the supercapacitor prepared by the conventional slurry coating method.

Shown in FIG. 8 are Ragone plots of lithium ion capacitor (LIC) cells containing activated exfoliated graphite worms as the cathode active material, prelithiated graphite particles as the anode active material, and lithium salt (LiPF₆)—PC/DEC as organic liquid electrolyte. The data are for both LICs, wherein the cathode is prepared by the presently invented electrolyte-worm compressing and consolidating method and those by the conventional slurry coating of electrodes. These data indicate that the gravimetric energy densities and power densities of the LIC cells prepared by the presently invented method are significantly higher than those of their counterparts prepared via the conventional method. Again, the differences are huge.

It is of significance to point out that reporting the energy and power densities per unit of active material weight alone on a Ragone plot, as did by many researchers, may not give a realistic picture of the performance of the assembled supercapacitor cell. The weights of other device components also must be taken into account. These overhead components, including current collectors, electrolyte, separator, binder, connectors, and packaging, are non-active materials and do not contribute to the charge storage amounts. They only add weights and volumes to the device. Hence, it is desirable to reduce the relative proportion of overhead component weights and increase the active material proportion. However, it has not been possible to achieve this objective using conventional supercapacitor production processes. The present invention overcomes this long-standing, most serious problem in the art of supercapacitors.

In a commercial supercapacitor having an electrode thickness of 150 μm, the weight of the active material (i.e. activated carbon) accounts for about 30% of the total mass of the packaged cell. Hence, a factor of 3 to 4 is frequently used to extrapolate the energy or power densities of the device (cell) from the properties based on the active material weight alone. In most of the scientific papers, the properties reported are typically based on the active material weight alone and the electrodes are typically very thin (<<100 μm, and mostly <<50 μm). The active material weight is typically from 5% to 10% of the total device weight, which implies that the actual cell (device) energy or power densities may be obtained by dividing the corresponding active material weight-based values by a factor of 10 to 20. After this factor is taken into account, the properties reported in these papers do not really look any better than those of commercial supercapacitors. Thus, one must be very careful when it comes to read and interpret the performance data of supercapacitors reported in the scientific papers and patent applications.

In conclusion, we have successfully developed an absolutely new, novel, unexpected, and patently distinct class of highly conducting graphite flake electrode materials and related processes of production. These electrodes, containing closely packed and highly oriented flakes of exfoliated graphite worms or expanded graphite interspaced with electrolyte, lead to exceptional supercapacitors exhibiting surprisingly high energy densities and power densities based on per unit of cell weight. 

What is claimed is:
 1. A process for producing a supercapacitor electrode containing electrolyte-impregnated flakes of exfoliated graphite worms or expanded graphite, said process comprising: (a) preparing a deformable mass of said flakes of exfoliated graphite worms or expanded graphite dispersed in or impregnated by a liquid or gel electrolyte; and (b) subjecting said deformable mass to a forced assembling and orientating procedure, forcing said deformable mass to form said electrode, wherein said flakes are spaced by thin electrolyte layers, having an electrolyte layer thickness from 0.4 nm to 10 nm, and said flakes are substantially aligned along a desired direction, and wherein said electrode has a physical density from 0.5 to 1.7 g/cm³ and a specific surface area from 50 to 3,300 m²/g, when measured in a dried state of said flakes without said electrolyte.
 2. The process of claim 1, wherein said step (a) further comprises a sub-step of subjecting said flakes of exfoliated graphite worms or expanded graphite to a chemical or physical activation treatment to obtain activated graphite flakes and then dispersing said activated graphite flakes in said liquid or gel electrolyte or impregnating said activated graphite flakes with said liquid or gel electrolyte.
 3. The process of claim 1, wherein said flakes are pre-deposited with a nanoscaled coating or particles of a redox pair partner, having a coating thickness or particle diameter less than 100 nm, selected from an intrinsically conductive polymer, a transition metal oxide, and/or an organic molecule, wherein said redox pair partner and said flakes form a redox pair for pseudo-capacitance.
 4. The process of claim 2, wherein said activated graphite flakes, prior to said dispersing or impregnating, are pre-deposited with a nanoscaled coating or particles of a redox pair partner, having a coating thickness or particle diameter less than 100 nm, selected from an intrinsically conductive polymer, a transition metal oxide, and/or an organic molecule, wherein said redox pair partner and said flakes form a redox pair for pseudo-capacitance.
 5. The process of claim 3, wherein said intrinsically conducting polymer is selected from polyaniline, polypyrrole, polythiophene, polyfuran, sulfonated polyaniline, sulfonated polypyrrole, sulfonated polythiophene, sulfonated polyfuran, sulfonated polyacetylene, or a combination thereof.
 6. The process of claim 4, wherein said intrinsically conducting polymer is selected from polyaniline, polypyrrole, polythiophene, polyfuran, sulfonated polyaniline, sulfonated polypyrrole, sulfonated polythiophene, sulfonated polyfuran, sulfonated polyacetylene, or a combination thereof.
 7. The process of claim 1, wherein said liquid electrolyte contains an aqueous electrolyte, an organic electrolyte, an ionic liquid electrolyte, or a mixture of an organic and an ionic electrolyte.
 8. The process of claim 1, wherein said flakes of exfoliated graphite worms or expanded graphite contain chemically or physically activated flakes.
 9. The process of claim 1, wherein said forced assembling and orientating procedure is conducted in the presence of a current collector, which current collector is embedded in said deformable mass or bonded to said deformable mass to form said supercapacitor electrode.
 10. The process of claim 1, wherein said forced assembling and orientating procedure includes introducing said deformable mass, having an initial volume V₁, in a mold cavity cell and driving a piston into said mold cavity cell to reduce the deformable mass volume to a smaller value V₂, allowing excess electrolyte to flow out of said cavity cell and aligning said flakes along a desired direction.
 11. The process of claim 1, wherein said forced assembling and orientating procedure includes introducing said graphene dispersion in a mold cavity cell having an initial volume V₁, and applying a suction pressure through a porous wall of said mold cavity to reduce the deformable mass volume to a smaller value V₂, allowing excess electrolyte to flow out of said cavity cell through said porous wall and aligning said flakes along a desired direction.
 12. The process of claim 1, wherein said forced assembling and orientating procedure includes introducing a first layer of said deformable mass onto a surface of a supporting conveyor and driving said layer of deformable mass supported on said conveyor through at least a pair of pressing rollers to reduce a thickness of said deformable mass layer and align said flakes along a direction parallel to said conveyor surface for forming a layer of electrolyte-impregnated flakes.
 13. The process of claim 12, further including a step of introducing a second layer of said deformable mass onto a surface of said layer of electrolyte-impregnated flakes to form a two-layer structure, and driving said two-layer structure through at least a pair of pressing rollers to reduce a thickness of said second layer of deformable mass and align said flakes along a direction parallel to said conveyor surface for forming a layer of electrolyte-impregnated flakes.
 14. The process of claim 1, further including a step of compressing or roll-pressing said electrolyte-impregnated flakes to reduce a thin electrolyte layer thickness in said impregnated flakes, improve orientation of flakes, and squeeze excess electrolyte out of said impregnated flakes for forming said supercapacitor electrode.
 15. The process of claim 12, which is a roll-to-roll process wherein said forced assembling and orientating procedure includes feeding said supporting conveyor, in a continuous film form, from a feeder roller to a deposition zone, continuously or intermittently depositing said deformable mass onto a surface of said supporting conveyor film to form said layer of electrolyte-impregnated flakes thereon, and collecting said layer of electrolyte-impregnated flakes supported on conveyor film on a collector roller.
 16. The process of claim 1, further comprising a step of cutting said electrolyte-impregnated flakes into multiple sheets and stacking said multiple sheets to form a supercapacitor electrode.
 17. The process of claim 1, further comprising a step of attaching said electrolyte-impregnated flakes to a current collector, wherein said flakes are aligned parallel to a primary surface of said current collector.
 18. The process of claim 1, further comprising a step of attaching said electrolyte-impregnated flakes to a current collector, wherein said flakes are aligned perpendicular to a primary surface of said current collector.
 19. A process of producing a supercapacitor electrode, comprising stacking a current collector with at least a layer of said electrolyte-impregnated flakes of claim 1 to form a multiple-layer structure and further comprising a step of compressing and consolidating said multi-layer structure to increase a physical density and decrease a thickness of said multi-layer structure to form said supercapacitor electrode.
 20. The process of claim 19, wherein at least one layer of said electrolyte-impregnated flakes is attached to one surface of said current collector and at least one layer of said electrolyte-impregnated flakes is attached to the opposing surface of said current collector prior to said step of compressing and consolidating.
 21. A supercapacitor comprising an anode, a cathode, an ion-permeable separator that electronically separates said anode and said cathode, and an electrolyte in ionic contact with said anode and said cathode, wherein the anode and/or the cathode contains the electrolyte-impregnated flakes of claim
 1. 22. The supercapacitor of claim 21, further comprising an anode current collector and/or a cathode current collector and said flakes in said electrolyte-impregnated flakes are parallel to a primary surface of said anode current collector or said cathode current collector.
 23. The supercapacitor of claim 21, further comprising an anode current collector and/or a cathode current collector and said flakes in said electrolyte-impregnated flakes are perpendicular to a primary surface of said anode current collector or said cathode current collector. 